Halogenated nitrobutadienes for controlling animal pests

ABSTRACT

The present invention relates to novel halonitrobutadienes, to processes for their preparation and to their use for controlling animal pests.

The present patent application has been filed under 35 U.S.C. 371 as anational stage application of PCT/EP02/11844, filed Oct. 23, 2002, whichwas published in German as International Patent Publication WO 03/040129on May 15, 2003, which is entitled to the right of priority of GermanPatent Application 101 54 313.1, filed Nov. 5, 2001.

The present invention relates to novel unsaturated compounds, toprocesses for their preparation and to their use for controlling animalpests.

Various halogen-substituted 1,3-butadienes, such as, for example,4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (Yu. A. Ol'dekop etal., Zh. Org. Khim. 15, 6, 1979, pp. 1321-1322; V. I. Potkin et al., Zh.Org. Khim. 31, 2, 1995, pp. 1816-1822),2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (Yu. A. Ol'dekop et al., Zh.Org. Khim. 12, 9, 1976, pp. 2039-2040; Potkin et al., Dokl. Nats. Akad.Nauk Belarusi 40, 1, 1996, pp. 68-71) or1,3-dinitro-1,2,4,4-tetrachloro-1,3-butadiene (N. I. Nechai et al.,Dokl. Nats. Akad. Nauk Belarusi 42, 2, 1989, pp. 75-78) are alreadyknown, and these compounds can be used as suitable starting materials inchemical synthesis (cf, for example, V. A. Zapol'ski et al., Russ. J.Org. Chem. 35, 3 1999, pp. 445-450).

It is also known that 1,1-bis(benzotriazol-1-yl)-,1,1-bis(3,5-dimethylpyrazol-1-yl)- and1,1-bis(1,2,4-triazol-1-yl)-2-nitrotrihalo-1,3-butadienes are highlyreactive (cf. V. A. Zapol'ski et al., Russ. J. Org. Chem. 33, 10, 1997,pp. 1461-1467; V. A. Zapol'ski et al., Russ. J. Org. Chem. 33, 11, 1997,pp. 1632-1637).

Furthermore, trichloronitrodieneaminoadamantane derivatives, such as,for example,1,1-bis-[1-(1-adamantyl)ethylamino]-3,4,4-trichloro-2-nitro-1,3-butadienehave already been described as compounds which have in vitro activityagainst tumours (cf. E. V. Vashkevich et al., Russ. J. Org. Chem. 35,12, 1999, pp. 1773-1776).

However, nothing has hitherto been disclosed about the use of thesecompounds as crop protecting agents and, in particular, for controllinganimal pests.

This invention now provides novel compounds of the formula (I)

in which

-   A represents in each case optionally substituted cycloalkyl,    heterocyclyl, aryl or hetaryl,-   R¹ represents hydrogen or alkyl,-   R² represents hydrogen or alkyl,-   Z represents halogen or NO₂,-   Hal represents halogen,-   X represents OR³, SR³ or NR⁴R⁵,-   Y represents hydrogen, halogen, OR⁶, SR⁶ or NR⁷R⁸,    -   R³ represents in each case optionally substituted alkyl,        alkenyl, cycloalkyl, cycloalkylalkyl, each of which is        optionally interrupted by one or more heteroatoms, or represents        in each case optionally substituted aryl, hetaryl, arylalkyl or        hetarylalkyl,    -   R⁴ and R⁵ independently of one another represent hydrogen,        represent in each case optionally substituted alkyl, alkenyl,        alkynyl, cycloalkyl, cycloalkylalkyl, alkoxycarbonyl, each of        which is optionally interrupted by one or more heteroatoms, or        represent in each case optionally substituted aryl, hetaryl,        arylalkyl or hetarylalkyl, or    -   R⁴ and R⁵ together with the nitrogen atom to which they are        attached represent an optionally substituted ring which is        optionally interrupted by one or more heteroatoms,    -   R⁶ represents in each case optionally substituted alkyl,        alkenyl, cycloalkyl, cycloalkylalkyl, each of which is        optionally interrupted by one or more heteroatoms, or represents        in each case optionally substituted aryl or arylalkyl,    -   R⁷ and R⁸ independently of one another represent in each case        optionally substituted alkyl, alkenyl, cycloalkyl,        cycloalkylalkyl, each of which is optionally interrupted by one        or more heteroatoms, or represent in each case optionally        substituted aryl, hetaryl, arylalkyl or hetarylalkyl, or    -   R⁷ and R⁸ together with the nitrogen atom to which they are        attached represent an optionally substituted ring which is        optionally interrupted by one or more heteroatoms, or-   R² and R³ together with the atoms linking them form an optionally    substituted ring which is optionally interrupted by one or more    heteroatoms, or-   R² and R⁵ together with the atoms linking them form an optionally    substituted ring which is optionally interrupted by one or more    heteroatoms.

Furthermore, it has been found that the compounds of the formula (I)according to the invention in which the radicals R² and R³ or R² and R⁵together with the atoms linking them form a ring and Y representshydrogen or chlorine are obtained when a compound of the formula (II)

in which

-   Y¹ represents hydrogen or chlorine-   Z represents chlorine, bromine or nitro    are reacted with a compound of the formula (III)

in which

-   D represents in each case optionally substituted —CH₂—CH₂— or    —CH₂—CH₂—CH₂—,-   B represents OH, SH or

-    and-   A and R¹ are as defined above,    giving compounds of the formula (Ia)

in which

-   A, R¹, D, Y¹ and Z are as defined above and-   B¹ represents O, S or

Furthermore, compounds of the formula (Ib)

in which

-   A, R¹, D, B¹ and Z are as defined above and-   Y² represents OR⁶, SR⁶ or NR⁷R⁸,    -   in which    -   R⁶, R⁷ and R⁸ are as defined above,        are obtained when compounds of the formula (Ia) in which-   Y¹ represents chlorine    are reacted with compounds of the formula (IV)    H—Y²  (IV)    in which-   Y² is as defined above.

Alkyl, alone or as a component of a radical in the general formulae,denotes straight-chain or branched alkyl having preferably 1 to 6, inparticular 1 to 4, carbon atoms. Methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl andethylbutyl may be mentioned by way of example.

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl andtert-butyl may be mentioned as being preferred.

Alkenyl, alone or as a component of a radical in the general formulae,denotes straight-chain or branched alkenyl having preferably 2 to 6, inparticular 2 to 4, carbon atoms. Vinyl, 2-propenyl, 2-butenyl,3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl,1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl may bementioned by way of example.

2-Propenyl, 2-butenyl and 1-methyl-2-propenyl may be mentioned as beingpreferred.

Alkynyl, alone or as a component of a radical in the general formulae,denotes straight-chain or branched alkynyl having preferably 2 to 6, inparticular 3 or 4, carbon atoms. Optionally substituted 2-propynyl,2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl,4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl,4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl may be mentioned byway of example.

2-Propynyl and 2-butynyl may be mentioned as being preferred.

Cycloalkyl, alone or as a component of a radical in the generalformulae, denotes mono-, bi- and tricyclic cycloalkyl having preferably3 to 10, in particular 3, 5 or 7 carbon atoms. Cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl,bicyclo[2.2.2]octyl and adamantyl may be mentioned by way of example.

Haloalkyl, alone or as a component of a radical in the general formulae,contains 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to9, in particular 1 to 5, identical or different halogen atoms,preferably fluorine, chlorine or bromine, in particular fluorine orchlorine. Trifluoromethyl, trichloromethyl, chlorodifluoromethyl,dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, pentafluoroethyl andpentafluoro-tert-butyl may be mentioned by way of example.

Alkoxy, alone or as a component of a radical in the general formulae,denotes straight-chain or branched alkoxy having preferably 1 to 6, inparticular 1 to 4, carbon atoms. Methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy and tert-butoxy may be mentioned by wayof example.

Alkoxyalkoxy, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched alkoxyalkoxy havingpreferably 2 to 6, in particular 2 to 4, carbon atoms. Optionallysubstituted methoxymethoxy, methoxyethoxy, methoxy-n-propoxy andethoxyisopropoxy may be mentioned by way of example.

Alkoxyalkoxyalkoxy, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched alkoxyalkoxyalkoxy havingpreferably 3 to 6, in particular 3 or 4, carbon atoms.Methoxymethoxyethoxy, methoxyethoxyethoxy and methoxyethoxy-n-propoxymay be mentioned by way of example.

Haloalkoxy, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched haloalkoxy havingpreferably 1 to 6, in particular 1 to 4, carbon atoms. Optionallysubstituted difluoromethoxy, trifluoromethoxy, trichloromethoxy,chlorodifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy,2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy and2-chloro-1,1,2-trifluoroethoxy may be mentioned by way of example.

Alkylthio, alone or as a component of a radical in the general formulae,denotes straight-chain or branched alkylthio having preferably 1 to 6,in particular 1 to 4, carbon atoms. Methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio andtert-butylthio may be mentioned by way of example.

Haloalkylthio, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched haloalkylthio havingpreferably 1 to 6, in particular 1 to 4, carbon atoms.Difluoromethylthio, trifluoromethylthio, trichloromethylthio,chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio,2,2-difluoroethylthio, 1,1,2,2-tetrafluoroethylthio,2,2,2-trifluoroethylthio and 2-chloro-1,1,2-trifluoroethylthio may bementioned by way of example.

Alkylcarbonyl, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched alkylcarbonyl havingpreferably 1 to 6, in particular 1 to 4, carbon atoms in the alkylmoiety. Optionally substituted methylcarbonyl, ethylcarbonyl,n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl andtert-butylcarbonyl may be mentioned by way of example.

Cycloalkylcarbonyl, alone or as a component of a radical in the generalformulae, denotes mono-, bi- and tricyclic cycloalkylcarbonyl havingpreferably 3 to 10, in particular 3, 5 or 7, carbon atoms in thecycloalkyl moiety. Cyclopropylcarbonyl, cyclobutylcarbonyl,cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl,cycloheptylcarbonyl, cyclooctylcarbonyl, bicyclo[2.2.1]heptylcarbonyl,bicyclo[2.2.2]octylcarbonyl and adamantylcarbonyl may be mentioned byway of example.

Alkoxycarbonyl, alone or as a component of a radical in the generalformulae, denotes straight-chain or branched alkoxycarbonyl havingpreferably 1 to 6, in particular 1 to 4, carbon atoms in the alkoxymoiety. Methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl and tert-butoxycarbonyl may be mentioned by way ofexample.

Aryl is, for example, a mono-, di- or polycyclic aromatic radical, suchas phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, preferablyphenyl or naphthyl, in particular phenyl.

In the general formulae, arylalkyl preferably denotes arylalkyl havingpreferably 6 or 10, in particular 6, carbon atoms in the aryl moiety(preferably phenyl or naphthyl, in particular phenyl), and preferably 1to 4, in particular 1 or 2, carbon atoms in the alkyl moiety, where thealkyl moiety may be straight-chain or branched and the aryl moietyand/or alkyl moiety is preferably optionally substituted. Benzyl and1-phenylethyl may be mentioned by way of example and by way ofpreference.

The optionally substituted radicals of the general formulae may carryone or more, preferably 1 to 3, in particular 1 or 2, identical ordifferent substituents. The following substituents may be mentioned byway of example and by way of preference:

Alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl andtert-butyl; alkoxy having preferably 1 to 4, in particular 1 or 2,carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy; alkylthio, such as methylthio,ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio,sec-butylthio; haloalkyl having preferably 1 to 5, in particular 1 to 3,halogen atoms, where the halogen atoms are identical or different andare preferably fluorine, chlorine or bromine, in particular fluorine orchlorine, such as difluoromethyl, trifluoromethyl, trichloromethyl;hydroxyl; halogen, preferably fluorine, chlorine, bromine and iodine, inparticular fluorine and chlorine; cyano; nitro; amino; monoalkyl- anddialkylamino having preferably 1 to 4, in particular 1 or 2, carbonatoms per alkyl group, such as methylamino, methylethylamino,dimethylamino, n-propylamino, isopropylamino, methyl-n-butylamino;alkylcarbonyl radicals, such as methylcarbonyl; alkoxycarbonyl havingpreferably 2 to 4, in particular 2 or 3, carbon atoms, such asmethoxycarbonyl and ethoxycarbonyl; alkylsulphinyl having 1 to 4, inparticular 1 or 2, carbon atoms; haloalkylsulphinyl having 1 to 4, inparticular 1 or 2, carbon atoms and 1 to 5 halogen atoms, such astrifluoromethylsulphinyl; haloalkylsulphonyl having 1 to 4, inparticular 1 or 2, carbon atoms and 1 to 5 halogen atoms, such astrifluoromethylsulphonyl, perfluoro-n-butylsulphonyl,perfluoroisobutylsulphonyl; arylsulphonyl having preferably 6 or 10 arylcarbon atoms, such as phenylsulphonyl; acyl, aryl, aryloxy which fortheir part may carry one of the substituents mentioned above, and alsothe formimino radical (—HC═N—O-alkyl).

It is possible for two identical or different substituents to be presentat the same atom.

In mono- or dialkylamino groups, alone or as a component of a radical inthe general formulae, alkyl denotes straight-chain or branched alkylhaving preferably 1 to 6, in particular 1 to 4, carbon atoms. Examplesof substituted mono- or dialkylamino groups which may be mentioned aremethylamino, ethylamino, dimethylamino, diethylamino, di-n-propylamino,diisopropylamino and dibutylamino.

In mono- or dialkoxyalkylamino groups, alone or as a component of aradical in the general formulae, alkoxyalkyl denotes straight-chain orbranched alkoxyalkyl having preferably 2 to 6, in particular 2 to 4,carbon atoms. Examples of substituted mono- or dialkoxyalkylamino groupswhich may be mentioned are methoxymethylamino, methoxyethylamino,di(methoxymethyl)amino or di(methoxyethyl)amino.

Suitable cyclic amino groups are heteroaromatic or heteroaliphatic ringsystems having one or more nitrogen atoms as heteroatom, where theheterocycles may be saturated or unsaturated, may comprise one ringsystem or a plurality of fused ring systems and may optionally containfurther heteroatoms, such as, for example, one or two nitrogen, oxygenand sulphur, etc. Moreover, cyclic amino groups may also denote aspirocyclic ring or a bridged ring system. The number of atoms formingthe cyclic amino groups is not limited, in the case of a one-ringsystem, for example, the ring may comprise 3 to 8 atoms and in the caseof a three-ring system, the ring may comprise 7 to 11 atoms.

Examples of cyclic amino groups having saturated and unsaturatedmonocyclic groups and one nitrogen atom as heteroatom which may bementioned are 1-azetidinyl, pyrrolidino, 2-pyrrolin-1-yl, 1-pyrrolyl,piperidino, 1,4-dihydropyrazin-1-yl, 1,2,5,6-tetrahydropyrazin-1-yl,1,4-dihydropyridin-1-yl, 1,2,5,6-tetrahydropyridin-1-yl,homopiperidinyl; examples of cyclic amino groups having saturated andunsaturated monocyclic groups and two or more nitrogen atoms asheteroatoms which may be mentioned are 1-imidazolidinyl, 1-imidazolyl,1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 1-piperazinyl,1-homopiperazinyl, 1,2-dihydropyridazin-1-yl, 1,2-dihydropyrimidin-1-yl,perhydropyrimidin-1-yl, 1,4-diazacycloheptan-1-yl; examples of cyclicamino groups having saturated and unsaturated monocyclic groups and oneor two oxygen atoms and one to three nitrogen atoms as heteroatoms whichmay be mentioned are oxazolidin-3-yl, 2,3-dihydroisoxazol-2-yl,isoxazol-2-yl, 1,2,3-oxadiazin-2-yl, morpholino; examples of cyclicamino groups having saturated and unsaturated monocyclic groups and oneto three nitrogen atoms and one or two sulphur atoms as heteroatomswhich may be mentioned are thiazolidin-3-yl, isothiazolin-2-yl,thiomorpholino or dioxothiomorpholino; examples of cyclic amino groupshaving saturated and unsaturated condensed cyclic groups which may bementioned are indol-1-yl, 1,2-dihydrobenzimidazol-1-yl,perhydropyrrolo[1,2-a]-pyrazin-2-yl; an example of a cyclic amino grouphaving spirocyclic groups which may be mentioned is2-azaspiro[4,5]decan-2-yl; an example of a cyclic amino group havingbridged heterocyclic groups which may be mentioned is2-azabicyclo[2.2.1]heptan-7-yl.

The formula (I) provides a general definition of the compounds accordingto the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below.

-   A preferably represents optionally halogen- (fluorine-, chlorine-,    bromine-), cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-,    C₁-C₄-alkoxy- or C₁-C₄-haloalkoxy-substituted phenyl.-   A furthermore preferably represents pyrazolyl, 1,2,4-triazolyl,    oxazblyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl,    pyridyl, pyrazinyl or pyrimidinyl, which are optionally substituted    by fluorine, chlorine, bromine, cyano, nitro, C₁-C₂-alkyl (which is    optionally substituted by fluorine and/or chlorine), C₁-C₂-alkoxy    (which is optionally substituted by fluorine and/or chlorine),    C₁-C₂-alkylthio (which is optionally substituted by fluorine and/or    chlorine) or C₁-C₂-alkylsulphonyl (which is optionally substituted    by fluorine and/or chlorine).-   A furthermore preferably represents an optionally halogen- or    C₁-C₃-alkyl-substituted saturated C₅-C₆-cycloalkyl radical in which    optionally one methylene group is replaced by O or S.-   R¹ preferably represents hydrogen, methyl, ethyl, n-propyl or    i-propyl.-   R² preferably represents hydrogen, methyl, ethyl, n-propyl or    i-propyl.-   Hal preferably represents bromine or chlorine.-   X preferably represents OR³, SR³ or NR⁴R⁵.-   Y preferably represents hydrogen, halogen (in particular chlorine),    OR⁶, SR⁶ or NR⁷R⁸.-   Z preferably represents bromine, chlorine or nitro.-   R³ preferably represents straight-chain or branched C₁-C₆-alkyl,    C₃-C₆-alkenyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each    of which is optionally interrupted by oxygen or sulphur and    optionally substituted by halogen, hydroxyl or cyano, represents in    each case optionally C₁-C₄-alkyl-, C₁-C₂-haloalkyl-, halogen-,    C₁-C₄-alkoxy-, C₁-C₂-haloalkoxy-, nitro- or cyano-substituted    phenyl-C₁-C₂-alkyl, phenyl, pyridyl, thiazolyl, pyrazolyl or    pyrimidyl, or-   R² and R³ preferably represent an optionally C₁-C₄-alkyl-substituted    C₂-C₄-alkylidenediyl group.-   R⁴ and R⁵ preferably and independently of one another represent    hydrogen, represent straight-chain or branched C₁-C₆-alkyl,    C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₇-cycloalkyl,    C₃-C₇-cycloalkyl-C₁-C₆-alkyl, C₁-C₆-alkoxycarbonyl, each of which is    optionally interrupted by oxygen or sulphur and each of which is    optionally substituted by halogen, or represent in each case    optionally C₁-C₄-alkyl-, C₁-C₂-haloalkyl- or halogen-substituted    phenyl, phenyl-C₁-C₂-alkyl, pyridyl, thiazolyl, pyridyl-C₁-C₂-alkyl    or thiazolyl-C₁-C₂-alkyl.-   R⁴ and R⁵ furthermore preferably together with the N atom to which    they are attached represent a 4-, 5-, 6- or 7-membered ring or    represent a 7- to 10-membered bicycle which are optionally    interrupted by oxygen, sulphur, sulphoxyl, sulphonyl, carbonyl, N—R⁶    or by quaternized nitrogen and optionally substituted by    C₁-C₄-alkyl, or-   R² and R⁵ preferably together with the atoms linking them represent    an optionally C₁-C₄-alkyl-substituted saturated 5-, 6- or 7-membered    ring which, in addition to the two nitrogen atoms, contains no    further heteroatoms.-   R⁶ preferably represents straight-chain or branched C₁-C₆-alkyl,    C₃-C₆-alkenyl, C₅-C₇-cycloalkyl, C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each    of which is optionally interrupted by oxygen or sulphur and    optionally substituted by fluorine or chlorine, or represents in    each case optionally halogen-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,    C₁-C₂-haloalkyl-, C₁-C₂-haloalkoxy-, nitro- or cyano-substituted    phenyl-C₁-C₄-alkyl, pyridyl, thiazolyl-C₁-C₂-alkyl, phenyl, pyridyl,    pyrimidyl, thiazolyl.-   R⁷ and R⁸ preferably and independently of one another represent    straight-chain or branched C₁-C₆-alkyl, C₃-C₆-alkenyl,    C₃-C₇-cycloalkyl, C₃-C₇-cycloalkyl-C₁-C₆-alkyl, each of which is    optionally interrupted by oxygen or sulphur and optionally    substituted by fluorine or chlorine, represent in each case    optionally C₁-C₄-alkyl-, C₁-C₄-alkoxy-, halogen-, C₁-C₂-haloalkyl-,    C₁-C₄-haloalkoxy-, nitro- or cyano-substituted phenyl or    phenyl-C₁-C₂-alkyl.-   R⁷ and R⁸ furthermore preferably together with the N atom to which    they are attached represent a 4-, 5-, 6- or 7-membered ring or    represent a 7- to 11-membered bicycle which are optionally also    interrupted by oxygen, sulphur, sulphoxyl, sulphonyl, carbonyl,    —N—R⁶ or by quaternized nitrogen and optionally substituted by    C₁-C₄-alkyl.-   A particularly preferably represents thiazolyl or pyridyl which are    in each case optionally substituted by halogen (in particular    chlorine) or C₁-C₃-alkyl (in particular methyl).-   A furthermore particularly preferably represents an optionally    halogen- (in particular chlorine-) or C₁-C₃-alkyl- (in particular    methyl-) substituted tetrahydrofuryl radical.-   R¹ particularly preferably represents hydrogen or methyl.-   R² particularly preferably represents hydrogen, methyl or ethyl.-   Hal particularly preferably represents bromine or chlorine.-   X particularly preferably represents SR³ or NR⁴R⁵.-   Y particularly preferably represents hydrogen, chlorine, SR⁶ or    NR⁷R⁸.-   Z particularly preferably represents chlorine or nitro.-   R³ particularly preferably represents straight-chain or branched    C₁-C₄-alkyl, in particular methyl, ethyl, propyl, isopropyl,    isobutyl, sec-butyl, tert-butyl, hydroxy-C₁-C₄-alkyl, in particular    2-hydroxyethyl, 3-hydroxypropyl, C₃-C₄-alkenyl, in particular    2-propenyl, 2-butenyl, C₅-C₇-cycloalkyl, in particular cyclopentyl,    cyclohexyl, C₃-C₇-cycloalkyl-C₁-C₂-alkyl, in particular    cyclopropylmethyl, in each case optionally fluorine-, chlorine-,    bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₂-haloalkyl-,    C₁-C₂-haloalkoxy-, nitro- or cyano-substituted phenyl or benzyl, or-   R² and R³ particularly preferably represent a C₂-C₃-alkylidenediyl    group.-   R⁴ and R⁵ particularly preferably and independently of one another    represent hydrogen, straight-chain or branched C₁-C₄-alkyl or    C₁-C₄-haloalkyl, in particular methyl, ethyl, propyl, isopropyl,    trifluoroethyl, 1,1,1-trifluoroisopropyl, C₃-C₄-alkenyl, in    particular 2-propenyl, 2-butenyl.-   R⁴ and R⁵ furthermore particularly preferably represent    C₄-C₆-alkylidenediyl which is optionally substituted by methyl or    ethyl and optionally interrupted by oxygen, sulphur or N—R⁶, and in    particular together with the N atom to which they are attached    represent pyrrolidino, morpholino, thiomorpholino, piperidino,    imidazolo or piperazino, or-   R² and R⁵ particularly preferably together with the atoms linking    them represent a saturated 5-, 6- or 7-membered ring which, in    addition to the two nitrogen atoms, contains no further heteroatoms.-   R⁶ particularly preferably represents straight-chain or branched    C₁-C₄-alkyl, in particular methyl, ethyl, propyl, isopropyl,    n-butyl, isobutyl, sec-butyl, tert-butyl, allyl, or represents in    each case optionally fluorine-, chlorine-, bromine-, C₁-C₄-alkyl-,    C₁-C₂-alkoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or    nitro-substituted phenyl or benzyl.-   R⁷ and R⁸ particularly preferably and independently of one another    represent straight-chain or branched C₁-C₄-alkyl, in particular    methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,    tert-butyl, C₃-C₄-alkenyl, in particular 2-propenyl, 2-butenyl,    C₃-C₇-cycloalkyl, in particular cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl or cycloheptyl,    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, in particular cyclopropylmethyl,    cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl or    cycloheptylmethyl, or represent in each case optionally nitro-,    cyano-, halogen-, in particular bromine-, chlorine- or fluorine-,    C₁-C₄-alkyl-, in particular methyl-, C₁-C₄-haloalkyl-, in particular    trifluoromethyl-, C₁-C₄-alkoxy-, in particular methoxy-, or    halo-C₁-C₂-alkoxy-, in particular trifluoromethoxy-, substituted    phenyl or benzyl.-   R⁷ and R⁸ furthermore particularly preferably together with the N    atom to which they are attached represent a 5-, 6- or 7-membered    ring or represent a 7- to 11-membered bicycle which are optionally    also interrupted by oxygen, sulphur, carbonyl, N-methyl, N-ethyl,    N-allyl, N-phenyl, N-chlorophenyl, N-benzyl and optionally    substituted by methyl or ethyl.-   A very particularly preferably represents one of the radicals

-   R¹ very particularly preferably represents hydrogen or methyl.-   R² very particularly preferably represents hydrogen or methyl.-   Hal very particularly preferably represents bromine or chlorine, in    particular chlorine.-   X very particularly preferably represents SR³ or NR⁴R⁵.-   Y very particularly preferably represents chlorine, SR⁶ or NR⁷R⁸.-   Z very particularly preferably represents chlorine.-   R³ very particularly preferably represents methyl or phenyl.-   R² and R³ very particularly preferably represent a    C₂-C₃-alkylidenediyl group.-   R⁴ and R⁵ very particularly preferably and independently of one    another represent hydrogen, methyl or ethyl, or-   R² and R⁵ very particularly preferably together with the atoms    linking them represent a saturated 5- or 6-membered ring which, in    addition to the two nitrogen atoms, contains no further heteroatoms.-   R⁶ very particularly preferably represents straight-chain or    branched C₁-C₄-alkyl, in particular methyl, ethyl, propyl,    isopropyl, isobutyl, sec-butyl, tert-butyl, allyl or represents in    each case optionally fluorine-, chlorine-, bromine-, methyl-,    ethyl-, isopropyl-, tert-butyl-, methoxy-, trifluoromethyl-,    trifluoromethoxy-, cyano- or nitro-substituted phenyl or benzyl.-   R⁷ and R⁸ very particularly preferably and independently of one    another represent straight-chain or branched C₁-C₄-alkyl, in    particular methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl,    tert-butyl, C₃-C₄-alkenyl, in particular 2-propenyl, 2-butenyl,    C₃-C₇-cycloalkyl, in particular cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl or cycloheptyl,    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, in particular cyclopropylmethyl,    cyclopentylmethyl or cyclohexylmethyl, phenyl-C₁-C₂-alkyl, nitro, or    represent in each case optionally cyano-, methyl-, ethyl-,    isopropyl-, tert-butyl-, bromine-, chlorine-, fluorine- or    trifluoromethoxy-substituted phenyl or benzyl.-   R⁷ and R⁸ furthermore very particularly preferably together with the    N atom to which they are attached represent a 5-, 6- or 7-membered    ring or represent a 7- to 11-membered bicycle which are optionally    also interrupted by oxygen, sulphur, carbonyl, N-methyl, N-ethyl,    N-allyl, N-phenyl, N-chlorophenyl, N-benzyl and optionally    substituted by methyl.

In a particular group of compounds of the formula (I), A represents

In a further particular group of compounds of the formula (I), Arepresents

In a further particular group of compounds of the formula (I), Arepresents

In a further group of particular compounds, R¹ represents hydrogen.

In a further group of particular compounds, Z represents chlorine.

In a further group of particular compounds, Hal represents chlorine.

In a further particular group of compounds of the formula (I),

-   R² and X represent a radical —CH₂—CH₂—S—.

In a further particular group of compounds of the formula (I),

-   R² and X represent a radical —CH₂—CH₂—NH—.

In a further particular group of compounds of the formula (I),

-   R² and X represent a radical —CH₂—CH₂—CH₂—S—.

In a further particular group of compounds of the formula (I),

-   R² and X represent a radical —CH₂—CH₂—CH₂—NH—.

In a further particular group of compounds of the formula (I), Yrepresents NR⁷R⁸ and

-   R⁷ and R⁸ together with the nitrogen atom to which they are attached    represent a 5-, 6- or 7-membered ring which is optionally    interrupted by oxygen, sulphur or N—R⁶.

The general or preferred radical definitions or illustrations listedabove apply both to the end products and, correspondingly, to startingmaterials and intermediates. These radical definitions can be combinedwith one another as desired, i.e. including combinations between therespective preferred ranges.

Preference according to the invention is given to compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred.

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

In the radical definitions given above and below, hydrocarbon radicals,such as alkyl, are in each case straight-chain or branched as far asthis is possible—including in combination with heteroatoms, such as inalkoxy.

The compounds of the general formula (I) are novel; they can beprepared, for example, by the processes given above.

Below, the processes according to the invention are illustrated usingselected examples (cf. also the Preparation Examples).

If, in the process according to the invention for preparing the novelunsaturated compounds of the general formula (Ia),2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene is used as compound of thegeneral formula (II) andN-(6-chloropyridin-3-ylmethyl)-ethylene-1,2-diamine (R¹:2-chloropyrid-5-yl; A: —H; D: —CH₂—CH₂—; B: —NH₂) is used as aminocompound of the general formula (III), the process can be represented byreaction scheme I below:

If halogen-substituted 1,3-butadienes of the general formula (II) areused, the process according to the invention may, if appropriate, affordthe compounds of the general formula (I) as a mixture of E and Zisomers.

The formula (II) provides a general definition of thehalogen-substituted 1,3-butadienes required as starting materials forcarrying out the process according to the invention.

The halogen-substituted 1,3-butadienes used as starting materials areknown (cf. Yu. A. Ol'dekop et al., Zh. Org. Khim. 15, 6, 1979, p.1321-1322; V. 1. Potkin et al., Zh. Org. Khim. 31, 2, 1995, p.1816-1822; Yu. A. Ol'dekop et al., Zh. Org. Khim. 12, 9, 1976, p.2039-2040; Potkin et al., Dokl. Nats. Akad. Nauk Belarusi 40, 1, 1996,p. 68-71; N. I. Nechai et al., Dokl. Nats. Akad. Nauk Belarusi 42, 2,1998, p. 75-78).

The general formula (III) provides a definition of the compoundsfurthermore to be used as starting materials for carrying out theprocess according to the invention.

In this formula (III), A, B, D and R¹ are as defined above.

Some of the compounds of the general formula (III) are known, and theycan be obtained by known methods (cf., for example, hydroxy compoundswhere B=OH: EP 192060; mercapto compounds where B=SH: Jap-Pat. 05070431;amino compounds where B=NHR⁴: DE-A 19710613, JP-Pat. 07242633, JP-Pat.06016636, JP-Pat. 05310697, JP-Pat. 04217957, EP 609811, EP 542086, EP474057, EP 163855; S. Kagabu et al., Biosci., Biotechnol., Biochem. 62,6, 1998, p. 1216-1224).

In general, it is advantageous to carry out the reaction of thehalogen-substituted 1,3-butadienes of the general formula (II) with thecompounds of the general formula (III) in the presence of diluents.Diluents are advantageously employed in such an amount that the reactionmixture remains readily stirrable during the entire process. Suitablediluents for carrying out the process according to the invention are allorganic solvents which are inert to the reactants.

Examples which may be mentioned are: halogenated hydrocarbons, inparticular chlorinated hydrocarbons, such as tetrachloroethylene,tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane,chloroform, carbon tetrachloride, trichloroethane, trichloroethylene,pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene,bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene;alcohols, such as methanol, ethanol, isopropanol, tert-butanol; ethers,such as ethyl propyl ether, methyl tert-butyl ether, methyl-n-butylether, anisole, phenetol, cyclohexyl methyl ether, dimethyl ether,diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether,diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether,tetrahydrofuran, dioxane, dichlorodiethyl ether and polyethers ofethylene oxide and/or propylene oxide; nitrohydrocarbons, such asnitromethane, nitroethane, nitropropane, nitrobenzene,chloronitrobenzene, o-nitrotoluene; nitriles, such as acetonitrile,propionitrile, butyronitrile, isobutyronitrile, benzonitrile,m-chlorobenzonitrile, and also compounds such as tetrahydrothiophenedioxide and dimethyl sulphoxide, tetramethylene sulphoxide, dipropylsulphoxide, benzyl methyl sulphoxide, diisobutyl sulphoxide, dibutylsulphoxide, diisoamyl sulphoxide; sulphones, such as dimethyl sulphone,diethyl sulphone, dipropyl sulphone, dibutyl sulphone, diphenylsulphone, dihexyl sulphone, methyl ethyl sulphone, ethyl propylsulphone, ethyl isobutyl sulphone and pentamethylene sulphone;aliphatic, cycloaliphatic or aromatic hydrocarbons, such as pentane,hexane, heptane, octane, nonane and technical-grade hydrocarbons, forexample white spirits with components having boiling points in the rangeof, for example, from 40° C. to 250° C., cymene, petroleum fractionshaving a boiling point in the range from 70° C. to 190° C., cyclohexane,methylcyclohexane, petroleum ether, ligroin, octane, benzene, toluene,chlorobenzene, bromobenzene, nitrobenzene, xylene; esters, such asmethyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and alsodimethyl carbonate, dibutyl carbonate, ethylene carbonate; amides, suchas hexamethylphosphoric triamide, formamide, N-methylformamide,N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dipropylformamide,N,N-dibutylformamide, N-methylpyrrolidone, N-methylcaprolactam,1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine, octylpyrrolidone,octylcaprolactam, 1,3-dimethyl-2-imidazolinedione, N-formylpiperidine,N,N′-1,4-diformylpiperazine; ketones, such as acetone, acetophenone,methyl ethyl ketone, methyl butyl ketone.

The process according to the invention can of course also be carried outusing mixtures of the solvents and diluents mentioned.

However, preferred diluents for carrying out the process according tothe invention are nitriles, such as acetonitrile, propionitrile,butyronitrile or isobutyronitrile, in particular acetonitrile orpropionitrile, esters, such as methyl acetate, ethyl acetate, butylacetate, isobutyl acetate, in particular methyl acetate and ethylacetate, amides, such as N,N-dimethylformamide, N,N-dimethylacetamide,N,N-dipropylformamide, N,N-dibutylformamide, N-methylpyrrolidone, inparticular N,N-dimethylformamide, N,N-dimethylacetamide andN-methylpyrrolidone, alcohols, such as methanol, ethanol, isopropanol,tert-butanol, in particular methanol, ethers, such as ethyl propylether, methyl tert-butyl ether, cyclohexyl methyl ether, dimethyl ether,diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, inparticular methyl tert-butyl ether, tetrahydrofuran and dioxane, andalso dimethyl sulphoxide.

The conversion of compounds of the general formula (II) by the processaccording to the invention is carried out by reacting thehalogen-substituted 1,3-butadienes of the general formula (II) in thepresence of a compound of the general formula (III) in one of thediluents stated.

The reaction time is from 10 minutes to 48 hours. The reaction iscarried out at temperatures between −100° C. and +70° C., preferablybetween −78° C. and +50° C., particularly preferably between −50° C. and+30° C. In principle, it is possible to operate under atmosphericpressure. The reaction is preferably carried out under atmosphericpressure and, if appropriate, under an atmosphere of protective gas(nitrogen or argon). However, it is also possible to operate underelevated pressure.

For carrying out the process according to the invention, in general from0.5 to 4.0 mol, preferably from 1.0 to 3.5 mol, particularly preferablyfrom 1.5 to 2.5 mol, of a compound of the general formula (III) areemployed per mole of halogen-substituted 1,3-butadiene of the generalformula (II).

After the reaction is ended, the reaction products are separated in acustomary manner. They can be purified by recrystallization, vacuumdistillation or column chromatography (cf. also the PreparationExamples).

If, in the processes according to the invention for preparing the novelunsaturated compounds of the general formula (Ib), the compound of thegeneral formula (Ia) used is the2-chloro-5-[2-(2,3,3-trichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]-pyridineobtained beforehand and the amino compound of the general formula (IV)used is thiomorpholine (Y²: NR⁷R⁸, where R⁷-R⁸: —CH₂—CH₂—S—CH₂—CH₂), theprocess can be represented by reaction scheme II below:

If halogen-substituted 1,3-butadienes of the general formula (Ia) areused, the process according to the invention may, if appropriate, affordthe compounds of the general formula (Ib) as a mixture of E and Zisomers.

The formula (Ia) provides a general definition of thehalogen-substituted 1,3-butadienes required as starting materials forcarrying out the process according to the invention.

In this formula (Ia), Y¹ represents halogen, in particular chlorine.

The halogen-substituted 1,3-butadienes used as starting materials can beobtained by the process mentioned above.

The general formula (IV) provides a definition of the compoundsfurthermore to be used as starting materials for carrying out theprocess according to the invention.

Some of the compounds of the general formula (IV) are known, some arecommercially available, and they can be prepared by known methods (cf.,for example, reactions for preparing alcohols, sulphur compounds andorganic nitrogen compounds in “Reaktionen der organischen Synthese”[Reactions of Organic Synthesis], C. Ferri, Georg Thieme VerlagStuttgart 1978, p. 375-384; p. 462-468 and p. 496-512; Organikum, JohannAmbrosius Barth Leipzig-Berlin-Heidelberg, Ed. Deutscher Verlag derWissenschaften, Literature references on p. 228 and p. 229).

In general, it is advantageous to carry out the reaction of thecompounds of the general formula (Ia) with the compounds of the generalformula (IV) in the presence of diluents. Diluents are preferablyemployed in such an amount that the reaction mixture remains readilystirrable during the entire process. Suitable diluents for carrying outthe process according to the invention are all of the inert organicsolvents mentioned above.

However, preferred diluents for carrying out the process according tothe invention are nitriles, such as acetonitrile, propionitrile,butyronitrile, isobutyronitrile, in particular acetonitrile orpropionitrile, amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide,N-methylpyrrolidone, in particular N,N-dimethylformamide,N,N-dimethylacetamide and N-methylpyrrolidone, alcohols, such asmethanol, ethanol, isopropanol, tert-butanol, in particular methanol,and also dimethyl sulphoxide.

The reaction of compounds of the general formula (Ia) by the processaccording to the invention is carried out by reacting the compounds ofthe general formula (Ia) in the presence of a compound of the generalformula (IV) in one of the diluents mentioned.

The reaction time is from 10 minutes to 48 hours. The reaction iscarried out at temperatures between −70° C. and +200° C., preferablybetween −30° C. and +150° C., particularly preferably between 0° C. and+100° C. In principle, it is possible to operate under atmosphericpressure. The process is preferably carried out under atmosphericpressure and, if appropriate, under an atmosphere of protective gas(nitrogen or argon). However, it is also possible to operate underelevated pressure.

For carrying out the process according to the invention, in general from1.0 to 5.0 mol, preferably from 1.5 to 4.5 mol, particularly preferablyfrom 2.0 to 3.5 mol, of a compound of the general formula (V) areemployed per mole of halogen-substituted 1,3-butadiene of the generalformula (Ia).

After the reaction is ended, the reaction products are separated in acustomary manner. They can be purified in a customary manner byrecrystallization, vacuum distillation or column chromatography (cf.also the Preparation Examples).

The active compounds are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector, and have good plant tolerance andfavourable toxicity to warm-blooded animals. They may preferably beemployed as plant protection agents. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The above-mentioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides ormicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and including the plant cultivars protectable or not protectableby plant breeders' rights. Plant parts are to be understood as meaningall parts and organs of plants above and below the ground, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stalks, stems, flowers, fruit bodies, fruits and seedsand also roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and plant partswith the active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is to say liquid solventsand/or solid carriers, optionally with the use of surfactants, that isto say emulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable Solid Carriers Are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, and also synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam-formers are: for example nonionic and anionic emulsifiers,such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and also protein hydrolysates; suitabledispersants are: for example lignosulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations, including mixtures with known fungicides,bactericides, acaricides, nematicides or insecticides, so as, forexample, to broaden the spectrum of action or prevent resistancesdeveloping. In many cases here, synergistic effects are obtained, i.e.the activity of the mixture is greater than the activity of theindividual components.

Suitable co-components are, for example, the following compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferinizone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, fumnecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irumnamycin, isoprothio lane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim,    probenazole, prochloraz, procymidone, propamocarb,    propanosine-sodium, propiconazole, propineb, pyraclostrobin,    pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadirnefon,    triadirnenol, triazbutil, triazoxide, trichlamide, tricyclazole,    tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705,-   OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-β-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)ethyl]amino]carbonyl]propyl}carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methy-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methylcyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,    2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4(1,1-dimethylpropyl)-phenyl]-2-methylpropyl]-2,6-dimethyl-morpholine    hydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium bicarbonate,-   methanetetrathiol-sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methaneimidamide,-   N-formyl-N-hydroxy-DL-alanine-sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran-3′-one,-   4-[3,4-dimethoxyphenyl-3-(4-fluorophenyl)-acryloyl]-morpholine.    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhiinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alphacypermethrin, alphamethrin, amitraz, avermectin, AZ    60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin,    bistrifluron, BPMC, bromophos A, bufencarb, buprofezin, butathiofos,    butocarboxim, butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin,    clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,    cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,    cypermethrin, cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, dicofol, diflubenzuron, dimethoate,    dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,    etoxazole, etrimfos,-   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,    fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,    fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam,    fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,    flufenoxuron, flumethrin, flutenzine, fluvalinate, fonophos,    fosmethilan, fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion,    ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, Metharhizium    anisopliae, Metharhizium flavoviride, methidathion, methiocarb,    methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,    mevinphos, milbemectin, milbemycin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propargite, propoxur, prothiofos, prothoate, pymetrozine,    pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion,    pyrimidifen, pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep,    sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, tetradifon, thetacypermethrin, thiacloprid,    thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,    thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,    triarathene, triazamate, triazophos, triazuron, trichlophenidine,    trichlorfon, triflumuron, trimethacarb,-   vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl    3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate,-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl[2-[[1,6-dihydro-6-oxo-1-(phenyhnethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   N-cyanomethyl-4-trifluoromethyl-nicotinamide,-   3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)-propoxy]-benzene.

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth regulators.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, ina mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andparts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineering,if appropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingnew properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. These can bevarieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichextend beyond the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (i.e. those obtainedby genetic engineering) which are to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particular advantageous usefulproperties (“traits”) to these plants. Examples of such properties arebetter plant growth, increased tolerance to high or low temperatures,increased tolerance to drought or to water or soil salt content,increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed in the plants by the genetic material from Bacillus thuringiensis(for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA,CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are alsoparticularly emphasized are the increased defence of plants againstfungi, bacteria and viruses by systemic acquired resistance (SAR),systemin, phytoalexins, elicitors and resistance genes andcorrespondingly expressed proteins and toxins. Traits that arefurthermore particularly emphasized are the increased tolerance of theplants to certain herbicidally active compounds, for exampleimidazolinones, sulphonylureas, glyphosate or phosphinotricin (forexample the “PAT” gene). The genes which impart the desired traits inquestion can also be present in combinations with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars having these or still to bedeveloped genetic traits, which plants will be developed and/or marketedin the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula I or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattella germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and aspreferences—but without a limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec. and Dinoderus minutus.

Hymenopterons, such as

-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus    augur.

Termites, such as

-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and    Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising it are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden window frames and doors, plywood,    chipboard, joinery or wooden products which are used quite generally    in house-building or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyestuffs and pigments, and also other processingauxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be protected.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, provided that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or a drying vegetable oil. Alkydresins having an oil content of more than 45% by weight, preferably 50to 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Very particularly preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyfenozideand triflumuron,

-   and also fungicides, such as epoxyconazole, hexaconazole,    azaconazole, propiconazole, tebuconazole, cyproconazole,    metconazole, imazalil, dichlorfluanid, tolylfluanid,    3-iodo-2-propinyl butylcarbamate, N-octyl-isothiazolin-3-one and    4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, in particular hulls, screens, nets, buildings,moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)-tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as

-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as

-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;

molluscicides such as

-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;

or conventional antifouling active compounds such as

-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed alone or in combination withother active compounds and auxiliaries in domestic insecticide productsfor controlling these pests. They are active against sensitive andresistant species and against all development stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus andDermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus andPolydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina and Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa and Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. andReticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp. andLiposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxyscalcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus and Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

They are used as aerosols, unpressurized spray products, for examplepump and atomizer sprays, automatic misting systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, unpowered or passive evaporation systems,moth papers, moth bags and moth gels, as granules or dusts, in baits forspreading or in bait stations.

PREPARATION EXAMPLES Example (I-1)

6.84 g (8.1 mmol) of a 22% strength aqueous solution ofN-(6-chloropyridin-3-ylmethyl)ethylene-1,2-diamine was concentrated toabout 3 g using a rotary evaporator, transferred into a 50 ml flaskusing 20 ml of MeOH and cooled to −40° C. Over a period of 3 min, asolution of 1 g (3.7 mmol) 2-nitropentachloro-1,3-butadiene in 10 ml ofMeOH was then added dropwise to this mixture, which was subsequentlystirred at −40° C. for 1 h and at room temperature for 1 h. Theresulting precipitate was filtered off with suction, washed with water(3×10 ml) and diethyl ether (3×10 ml) and dried under reduced pressure.This gave 0.42 g (30%) of2-chloro-5-[2-(2,3,3-trichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]pyridine.

Example (I-1) Alternative Preparation Method

At room temperature, 10 g (12 mmol) of a 22% strength aqueous solutionof N-(6-chloropyridin-3-ylmethyl)ethylene-1,2-diamine were added to asuspension of 1.08 g (3 mmol) of1-(4-methylphenylthio)-2-nitro-1,3,4,4-tetrachlorobuta-1,3-diene in 30ml of methanol, and this mixture was stirred at room temperature for 1day. The resulting1,1-bis-(4-methylphenylthio)-2-nitro-3,4,4-trichlorobuta-1,3-dieneprecipitate was filtered off, washed with water and cold methanol (2×3ml) and dried under reduced pressure. The yield was 0.27 g (20%). Thecombined filtrate was, at 0° C., neutralized with conc. HCl and, withstirring, mixed with 50 ml of water. The precipitate was filtered offwith suction, washed with water and ether (3×5 ml) and recrystallizedfrom methanol. This gave 0.13 g (15%) of2-chloro-5-[2,3,3-trichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]pyridine.

Example (I-2)

At room temperature, a solution of 0.35 g (4 mmol) of morpholine in 5 mlof MeOH was added dropwise to a suspension of 0.5 g (1.3 mmol) of2-chloro-5-[2-(2,3,3-trichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]pyridine(compound of Example (I-1)) in 20 ml of methanol (MeOH), and theresulting mixture was stirred at room temperature for 3 h and at 40-45°C. for 3 h. After cooling to 10° C., excess morpholine was neutralizedusing 5% HCl (to pH 6-7), 70 ml of water were then added with stirringand the resulting precipitate was filtered off with suction, washedthoroughly with water and dried initially on a glass frit and then underreduced pressure. This gave 0.34 g (60%) of2-chloro-5-[2-(2-morpholinyl-3,3-dichloro-1-nitro-allylidene)imidazolidin-1-ylmethyl]pyridine.

If, after mixing with water, the product separated out as an oil, thewater was decanted off and the oil was dissolved in 10 ml of MeOH andallowed to stand either in a fridge or in a steam cupboard. In mostcases, the product precipitates from methanol as a solid within 1-2days.

Example (I-3)

At 0° C., a solution of 0.08 g (1.5 mmol) of sodium methoxide in 5 ml ofmethanol was added to a suspension of 0.5 g (1.3 mmol) of2-chloro-5-[2-(2,3,3-trichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]pyridine(compound of Example (I-1)) and 0.17 g (1.4 mmol) of 4-methylthiophenolin 15 ml of methanol, and the mixture was stirred at room temperaturefor 2 h and at 35° C. for 10 h. After cooling to 50° C., 3 drops ofconc. HCl were added. The reaction mixture was then taken up in 50 ml ofice-water. The resulting precipitate was filtered off with suction andwashed with methanol (3×7 ml), petroleum ether (3×7 ml) and finally withwater. This gave 0.31 g (50%) of2-chloro-5-[2-(2-(p-tolylthio)-3,3-dichloro-1-nitroallylidene)imidazolidin-1-ylmethyl]pyridine.

The other compounds of the formula (I) listed in the table are obtainedin an analogous manner.

TABLE (I)

Ex. No. A R¹ R²  X Y Z Hal m.p. ° C. I-1

H CH₂—CH₂—NH Cl Cl Cl 174-175 I-2

H CH₂—CH₂—NH

Cl Cl 92-94 I-3

H CH₂—CH₂—NH

Cl Cl 204-206 I-4*

H CH₂—CH₂—NH Cl Cl Br 172-173 I-5

H CH₂—CH₂—NH H NO₂ Cl 150-152 I-6

H CH₂—CH₂—O Cl Cl Cl 156-158 I-7*

H

Cl Cl Cl 119-121 I-8

H CH₂—CH₂—NH

Cl Cl 130 I-9

H CH₂—CH₂—NH

Cl Cl 86-88 I-10

H CH₂—CH₂—NH

Cl Cl 80-82 I-11

H CH₂—CH₂—NH

Cl Cl  99-101 I-12

H CH₂—CH₂—NH

Cl Cl 105-107 I-13

H CH₂—CH₂—NH

Cl Cl 80-82 I-14

H CH₂—CH₂—NH

Cl Cl 134-135 I-15

H CH₂—CH₂—NH

Cl Cl 179-181 I-16

H CH₂—CH₂—NH Cl Cl Cl 153-154 I-17

H CH₂—CH₂—NH

Cl Cl 38-39 I-18

H CH₂—CH₂—NH

Cl Cl 150-151 I-19

H CH₂—CH₂—NH

Cl Cl 93-95 I-20

H CH₂—CH₂—NH

Cl Cl 63-65 I-21

H CH₂—CH₂—NH

Cl Cl 120-121 I-22

H CH₂—CH₂—CH₂—NH Cl Cl Cl 137-139 I-23

H CH₂—CH₂—CH₂—NH

Cl Cl 94-96 I-24

H CH₂—CH₂—CH₂—NH H NO₂ Cl 52-54 I-25

H CH₂—CH₂—NH H NO₂ Cl 150-152 I-26

H CH₂—CH₂—NH SCH₃ Cl Cl 84-86 I-27

H CH₂—CH₂—NH SCH₃ Cl Cl 111-113 I-28

H CH₂—CH₂—NH

Cl Cl 124-126 I-29

H CH₂—CH₂—NH

Cl Cl 136-137 I-30

H CH₂—CH₂—NCH3 Cl Cl Cl 153-154 I-31

H CH₂—CH₂—NH

Cl Cl 44-45 I-32

H CH₂—CH₂—NH

Cl Cl 155-156 I-33

H CH₂—CH₂—NH

Cl Cl viscousoil *is present as a Z,E isomer mixture

Example (II-1)

Z-1,3-Dinitro-1,4,4-trichloro-1,3-butadiene 1. Free-Radical Dimerizationof 1,2-dichloroethylene

100 g of 75% strength water-containing benzoyl peroxide are dissolved in0.5 l of 1,2-dichloroethylene (mixture of isomers, about 1:1, d²⁰=1.27g/ml), and the organic phase is separated off, dried over CaCl₂ andfinally transferred into a 2 l flask. A further 1.2 l of1,2-dichloroethylene are added, as well as 3-5 boiling stones, and themixture is heated under reflux for 30 d (about 10 h/d). (It is veryimportant to add 3-4 fresh boiling stones to the flask every day toensure uniform boiling of the mixture. It is recommended to monitor theevolution of CO₂ via a gas outlet at the reflux condenser). During thereaction, the boiling point of the reaction mixture increases by 10-15°C. When the reaction is ended, unreacted 1,2-dichloroethylene (about 1l) is removed under water pump vacuum and the reaction mixture thatremains is distilled under oil pump vacuum.

This gives about 1.25 kg (d²⁰=1.47 g/ml) of 1,3,4,4-tetrachloro-1-buteneas Z:E isomer mixture of about 3:7 (b.p. 78-82° C./1 mm Hg), yield(based on converted 1,2-dichloroethylene) 70%.

2. Bromination of 1,3,4,4-tetrachloro-1-butene

At 40-45° C., 90 ml of bromine are added dropwise over a period of 3 hto 300 g of 1,3,4,4-tetrachloro-1-butene (magnetic stirrer, irradiationwith a 100 W bulb), and the mixture is stirred at this temperature foranother 8 h. When the reaction has ended (TLC), 100 ml of 5% strengthNa₂S₂O₃ solution are added with stirring to the cooled reaction mixture,the mixture is stirred for 1 h and the organic phase(1,2-dibromo-1,3,4,4-tetrachlorobutane, about 500 g) is separated off,washed with water and used without additional purification for thedehydrohalogenation.

3. Dehydrohalogenation of 1,2-dibromo-1,3,4,4-tetrachlorbutane

At 10-15° C., a solution of 173 g of KOH and 20 g of TEBA in 300 ml ofwater is added dropwise with stirring over a period of 2 h to 500 g of1,2-dibromo-1,3,4,4-tetrachlorobutane, stirring is continued at roomtemperature for another 6 h, the reaction mixture is neutralized withconc. HCl, the product is extracted with chloroform and dried overCaCl₂, the solvents are removed using a rotary evaporator and themixture that remains is distilled under oil pump vacuum. This gives 237g of 1-bromo-1,4,4-trichloro-1,3-butadiene (E:Z=1:4), yield 71%.

4. Nitration of 1-bromo-1,4,4-trichloro-1,3-butadiene

Nitrating acid is prepared from 400 ml of 65% strength HNO₃ and 120 mlof conc. H₃PO₄, introduced into a 1 l two-necked flask fitted withground-joint stirrer, reflux condenser and dropping funnel and, withstirring, heated to 100-105° C. (the oil bath temperature must notexceed 115° C.). Over a period of 2 h, 230 g of1-bromo-1,4,4-trichloro-1,3-butadiene are then added dropwise to thenitrating acid, and the resulting mixture is stirred at an oil bathtemperature of 110-115° C. for another 1 h. After cooling to roomtemperature, the organic layer is separated off, the aqueous phase isextracted with petroleum ether (2×100 ml) and the combined organicphases are washed with water and dried using CaCl₂. The mixture isfiltered through a paper filter and cooled with stirring to −10-15° C.and the resulting precipitate is filtered off with suction and washedwith petroleum ether. This gives 43 g ofZ-1,3-dinitro-1,4,4-trichloro-1,3-butadiene (m.p. 70-71° C.), yield 18%.

Example II-2 Z,E-4-Bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene

1. Free-Radical Dimerization of Trichloroethylene

100 g of 75% strength water-containing benzoyl peroxide are dissolved in0.5 l of trichloroethylene (d₄ ²⁰=1.46 g/ml) and the organic phase isseparated off in a separating funnel, dried over CaCl₂ and thentransferred into a 2 l flask. A further 1.2 l of trichloroethylene and3-4 boiling stones are added, and the mixture is heated under reflux for12 d (about 10 h/d). (It is very important to add 3-4 fresh boilingstones to the flask every day to ensure uniform boiling of the mixture.It is recommended to monitor the evolution of CO₂ via a gas outlet atthe reflux condenser). During the reaction, the boiling point of thereaction mixture increases from 86° C. (pure trichloroethylene) to97-105° C. When the reaction is ended, unreacted trichloroethylene(about 1 l) is removed under water pump vacuum and the reaction mixturethat remains is distilled under oil pump vacuum. This gives about 0.87kg (about 0.52 l, d²⁰=1.67 g/ml) of 1,1,3,3,4,4-hexachloro-1-butene(b.p. 73-75° C./1 mm Hg), yield (based on converted trichloroethylene)85%.

2. Dechlorination of 1,1,3,3,4,4-hexachloro-1-butene

Over a period of 2 h, 67 g of Zn powder are added to a solution of 263 gof 1,1,3,3,4,4-hexachloro-1-butene in 200 ml of ethanol such that thereaction temperature does not exceed 60° C., stirring is continued at55-60° C. for another 5 h, the reaction mixture is cooled to roomtemperature, 500 ml of 1% strength HCl are added with stirring, themixture is extracted with chloroform and the extract is dried with CaCl₂and distilled under oil pump vacuum. This gives 173 g ofZ,E-1,1,3,4-tetrachloro-1,3-butadiene (b.p. 68-69° C./1 mm Hg), yield90%.

3. Bromination of 1,1,3,4-tetrachloro-1,3-butadiene

At 45-50° C., 26 ml of bromine are added dropwise over a period of 1 hto 96 g of 1,1,3,4-tetrachloro-1,3-butadiene (magnetic stirrer,irradiation with a 100 W bulb), and the mixture is stirred at thistemperature for another 12 h. When the reaction has ended (TLC), 40 mlof 5% strength Na₂S₂O₃ solution are added with stirring to the cooledreaction mixture, the mixture is stirred for 1 h and the organic phase(3,4-dibromo-1,1,3,4-tetrachloro-1-butane, about 167 g) is separatedoff, washed with water and used without additional purification for thedehydrobromination.

4. Dehydrobromination of 3,4-dibromo-1,1,3,4-tetrachloro-1-butene

At 10-15° C., a solution of 5.8 g of KOH and 0.5 g of TEBA in 30 ml ofwater is added dropwise with stirring over a period of 1 h to 35.2 g of3,4-dibromo-1,1,3,4-tetrachloro-1-butene, stirring is continued at roomtemperature for another 12 h and at 40-45° C. for 4 h, the reactionmixture is neutralized with conc. HCl, the product is extracted withchloroform and dried over CaCl₂, the solvents are removed using a rotaryevaporator and the mixture that remains is distilled under oil pumpvacuum. This gives 20.2 g ofZ,E-1-bromo-1,2,4,4-trichloro-1,3-butadiene, yield 75%.

5. Nitration of 1-bromo-1,2,4,4-tetrachloro-1,3-butadiene

Nitrating acid is prepared from 200 ml of 65% strength HNO₃ and 65 ml of98% strength H₂SO₄, introduced into a 0.5 l two-necked flask fitted withground-joint stirrer, reflux condenser and dropping funnel and, withstirring, heated to 95-100° C. (the oil bath temperature must not exceed110° C.). Over a period of 2 h, 136 g ofZ,E-1-bromo-1,2,4,4-trichloro-1,3-butadiene are then added dropwise tothe nitrating acid, and the resulting mixture is stirred at an oil bathtemperature of 100-105° C. for another 3 h. After cooling to roomtemperature, the organic layer is separated off, the aqueous phase isextracted with chloroform the combined organic phases are washed withwater, 5% strength NaHCO₃ solution and again water, dried using CaCl₂and distilled under reduced pressure. Bromodichloroacrolein is distilledoff as first fraction (about 4-8% of the total amount). The mainfraction comprises 71 g ofZ,E-4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene, yield 45%.

1-(4-Methylphenylthio)-2-nitro-1,3,4,4-tetrachlorobuta-1,3-diene

At room temperature, 4.72 g (38 mmol) of 4-methylthiophenol are added toa solution of 10.00 g (36.9 mmol) of 2-nitropentachloro-1,3-butadiene in20 ml of ether, and the mixture is stirred for 20 h. The ether is thenremoved under reduced pressure, and the crystal slurry which is formedafter addition of 20 ml of methanol is filtered off, washed with coldMeOH (2×10 ml) and dried under reduced pressure, yield 9.9 g (75%),R_(f)=0.72 (Et₂O: petroleum ether=1:3), m.p. 110-111° C.

1,1-Bis-(4-methylphenylthio)-2-nitro-3,4,4-trichlorobuta-1,3-diene

At 0° C., 5.05 g (75 mmol) of sodium ethoxide in 10 ml of ethanol areadded dropwise over a period of 10 min to a solution of 10.00 g (36.9mmol) of 2-nitropentachloro-1,3-butadiene and 9.3 g (75 mmol) of4-methylthiophenol in 50 ml of ethanol. After 2 h of stirring at 0° C.,the precipitate is separated off, washed with water and cold methanol(2×20 ml) and dried under reduced pressure, yield 14.5 g (88%),R_(f)=0.68 (Et₂O: petroleum ether=1:3), m.p. 117-118° C.

USE EXAMPLES Example A

Myzus Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Broad bean seedlings (Vicia faba minor) which are infested by the greenpeach aphid (Myzus persicae) are dipped into a preparation of activecompound of the desired concentration and placed into a plastic box.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity:

TABLE A Plant-damaging insects Myzus test Concentration of Kill rateactive compound in % after Active compounds in ppm 6^(d) (days) I-1 500100

according to the invention I-2 500 100

according to the invention

Example B

Phaedon Larvae Test

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity:

TABLE B Plant-damaging insects Phaedon larvae test Concentration ofactive compound Kill rate in % Active compounds in ppm after 6^(d)(days) I-2 100 100

according to the invention

Example C

Plutella Test

Solvent:   100 parts by weight of acetone 1 900 parts by weight ofmethanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and theconcentrate is diluted with methanol to the desired concentrations.

The stated amount of the preparation of active compound of the desiredconcentration is pipetted onto a standardized amount of synthetic feed.After the methanol has evaporated, about 200-300 eggs of the diamondbackmoth (Plutella xylostella) are placed onto the feed.

After the desired period of time, the kill of the eggs and/or larvae in% is determined. 100% means that all animals have been killed; 0% meansthat none of the animals have been killed.

In this test, for example, the activity of the following compounds ofthe Preparation Examples is superior to compounds of the prior art:

TABLE C Plant-damaging insects Plutella test Concentration of activecompound Kill rate in % Active compounds in ppm after 7^(d) (days) I-2150 100

according to the invention

Example D

Aphis gossypii Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cotton leaves (Gossypium hirsutum) which are heavily infested by thecotton aphid (Aphis gossypii) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity:

TABLE D Plant-damaging insects Aphis gossypii test Concentration ofactive compound Kill rate in % Active compounds in ppm after 6^(d)(days) I-2 500 100

according to the invention

Example E

Critical Concentration Test/Root-Systemic Action

Test insect: Aphis gossypii Solvent: 3.5 parts by weight of acetoneEmulsifier:   1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil of theinfected savoy cabbage plant. In this way, the active compound can betaken up from the soil by the roots of the plants and can be transportedinto the leaves. Here, the concentration of active compound in thepreparation is virtually immaterial, only the amount by weight pervolume unit of soil, which is stated in ppm (mg/ml), matters.

To demonstrate the root-systemic effect, evaluation is carried out after10 days by counting or estimating the number of dead animals. Theroot-systemic action of the active compound is derived from the killrate. It is 100% if all test animals have been killed and 0% if thenumber of test insects alive is the same as that for the untreatedcontrol.

Active compounds, application rates and results are shown in the tablebelow:

TABLE E Critical concentration test/root-systemic action Aphis gossypiiConcentration of Kill rate active compound in % after Active compoundsin ppm 10^(d) (days) I-1 20 100

according to the invention I-2 20 100

according to the invention

Example F

Critical Concentration Test/Root-Systemic Action

Test insect: Myzus persicae Solvent: 3.5 parts by weight of acetoneEmulsifier:   1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil of theinfected savoy cabbage plant. In this way, the active compound can betaken up from the soil by the roots of the plants and can be transportedinto the leaves. Here, the concentration of active compound in thepreparation is virtually immaterial, only the amount by weight pervolume unit of soil, which is stated in ppm (mg/ml), matters.

To demonstrate the root-systemic effect, evaluation is carried out after10 days by counting or estimating the number of dead animals. Theroot-systemic action of the active compound is derived from the killrate. It is 100% if all test animals have been killed and 0% if thenumber of test insects alive is the same as that for the untreatedcontrol.

Active compounds, application rates and results are shown in the tablebelow:

TABLE F Critical concentration test/root-systemic action Myzus persicaeConcentration of Kill rate active compound in % after Active compoundsin ppm 10^(d) (days) I-1 20 100

according to the invention I-2 20 100

according to the invention

Example G

Myzus Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea), which are heavily infested by thegreen peach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity:

TABLE G Plant-damaging insects Myzus test Concentration of activecompound Kill rate in % Active compounds in ppm after 6^(d) (days) I-2500 100

according to the invention I-11 500 100

according to the invention

Example H

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example, the activity of the following compounds ofthe Preparation Examples is superior to that of compounds of the priorart:

TABLE H Plant-damaging insects Phaedon larvae test Concentration ofactive compound Kill rate in % Active compounds in ppm after 6^(d)(days) I-2 500 100

according to the invention I-11 500 100

according to the invention

Example I

Bemisia Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentrations.

Cotton plants (Gossypium hirsutum) infected by eggs, larvae and pupae ofthe white fly (Bemisia tabaci) are dipped into a preparation of activecompound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

TABLE I Plant-damaging insects Bemisia test Concentration of activecompound Kill rate in % Active compounds in ppm after 6^(d) (days) I-2500 100

according to the invention I-10 500 100

according to the invention

Example J

Spodoptera frugiperda Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the armyworm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity:

TABLE J Plant-damaging insects Spodoptera frugiperda test Concentrationof active compound Rate of activity Active compounds in ppm after 7^(d)(days) 1-12 500 100

according to the invention

Example K

Critical Concentration Test/Root-Systemic Action

Test insect: Myzus persicae Solvent: 4 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is mixed intimately with the soil.Here, the concentration of the active compound in the preparation isvirtually immaterial, only the amount by weight of active compound pervolume unit of soil, which is stated in ppm (mg/ml) matters. The treatedsoil is filled into pots of a volume of 250 ml, and pregerminated broadbeans are planted into these pots. In this way, the active compound canbe taken up from the soil by the plant roots and be transported into theleaves.

To demonstrate the root-systemic effect, after 7 days, the plants arepopulated with the test animals mentioned above and, after a further 7days, evaluation is carried out by counting or estimating the number ofdead animals. The root-systemic action of the active compound is derivedfrom the kill rate. It is 100% if all test animals have been killed and0% if the number of test insects still alive is exactly the same as inthe untreated control.

Active compounds, application rates and results are shown in the tablebelow:

TABLE K Soil insects Critical concentration/root-systemic testConcentration of active compound in 4 ppm % Active compounds kill afterweeks I-1 2 3 4 5

100 100 99 100 according to the invention I-2 2 3 4

100 100 99 according to the invention

Example L

Test with Cat Fleas/Oral Uptake

Test animals: Adults of Ctenocephalides felis Solvent: Dimethylsulphoxide (DMSO)

To produce a suitable formulation, a suitable solution of activecompound is prepared from 20 mg of active compound and 1 ml of DMSO. 15μl of this formulation are added to 3 ml of citrated cattle blood andstirred.

10 unfed adult fleas (Ctenocephalides felis, strain “Georgi”) are placedinto a chamber (Ø 3.2 cm) whose top and bottom are closed with gauze. Ametal cylinder whose underside is covered with parafilm is placed ontothe chamber. The cylinder contains the 3 ml of blood/active compoundformulation which can be taken up by the fleas through the paraffinmembrane. Whereas the blood is warmed to 37° C., the temperature in thearea of the flea chambers is adjusted to 25° C. Controls are mixed withthe same volume of DMSO, without addition of a compound. Thedeterminations are carried out in triplicate.

After 28 h, the mortality in % (=dead fleas) is determined.

Compounds which effect at least 25% kill of the fleas within 28 h arejudged to be effective.

TABLE L Ctenocephalides felis, orally % Compound Concentration in ppmaction/kill I-4 100 40 I-3 100/20 50/0 I-2 100/20/4/0.8 80/80/0/0 I-10100/20 100/40 I-9 100/20  80/30 I-12 100/20  70/30 I-11 100/20 70/0 I-13100/20 100/20

Example M

Test with Flies (Musca domestica)

Test animals: adult Musca domestica, Reichswald strain (OP, SP,carbamate-resistant) Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution with dist. H₂O.

2 ml of this active compound preparation are pipetted onto filter paperdiscs (Ø 9.5 cm) in Petri dishes of corresponding dimensions. After thefilter discs have been dried, 25 test animals are transferred into thePetri dishes, which are then covered.

After 1, 3, 5, 24 and 48 hours, the activity of the active compoundpreparation is determined. 100% means that all flies have been killed;0% means that none of the flies have been killed.

In this test, for example, the activity of the following compounds ofthe Preparation Examples is superior to that of the compounds of theprior art:

TABLE M Musca domestica % Compound Concentration in ppm action/kill I-4100/20 100/0 I-2 100/20  50/0

Example N

Blowfly Larvae Test/Development-Inhibitory Action

Test animals: Lucilia cuprina larvae Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution with dist. H₂O.

About 20 Lucilia cuprina larvae are introduced into a test tube whichcontains about 1 cm³ of horse meat and 0.5 ml of the preparation ofactive compound to be tested. After 24 and 48 hours, the efficacy of thepreparation of active compound is determined. The test tubes aretransferred into a beaker whose bottom is covered with sand. After afurther 2 days, the test tubes are removed and the pupae are counted.

The efficacy of the preparation of active compound is assessed by thenumber of flies that have hatched after 1.5 times the period ofdevelopment of an untreated control. 100% means that no flies havehatched; 0% means that all flies have hatched normally.

In this test, for example, the activity of the following compounds ofthe Preparation Examples is superior to that of the compounds of theprior art:

TABLE N Lucilia cuprina (48 h) % Compound Concentration in ppmaction/kill I-1 100/20 100/0 I-2 100/20 100/0 I-12 100/20 100/0 I-11100/20 100/0 I-13 100/20 100/0

1. A compound of formula (I)

in which A represents optionally substituted six-membered heterocyclylor hetaryl containing a ring nitrogen atom, R¹ represents hydrogen oralkyl, R² represents hydrogen or alkyl, Z represents halogen or NO_(2,)Hal represents halogen, X represents OR³, SR³, or NR⁴R⁵, Y representshydrogen, halogen, OR⁶, SR⁶, or NR⁷R⁸, R³ represents optionallysubstituted alkyl, alkenyl, cycloalkyl, or cycloalkylalkyl; orrepresents optionally substituted aryl or arylalkyl, R⁴ and R⁵independently of one another represent hydrogen; represent optionallysubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, oralkoxycarbonyl; or represent optionally substituted aryl or arylalkyl;or R⁴ and R⁵ together with the nitrogen atom to which they are attachedrepresent an optionally substituted ring, R⁶ represents optionallysubstituted alkyl, alkenyl, cycloalkyl, or cycloalkylalkyl; orrepresents optionally substituted aryl or arylalkyl, and R⁷ and R⁸independently of one another represent optionally substituted alkyl,alkenyl, cycloalkyl, or cycloalkylalkyl; or represent optionallysubstituted aryl or arylalkyl, or R⁷ and R⁸ together with the nitrogenatom to which they are attached represent an optionally substituted ringthat is optionally interrupted by one or more heteroatoms selected fromthe group consisting of nitrogen, oxygen, and sulphur, or R² and R³together with the atoms linking them form an optionally substitutedring.
 2. A compound of formula (I) according to claim 1 in which Arepresents optionally substituted six-membered heterocyclyl containing aring nitrogen atom or optionally substituted hetaryl wherein the hetarylgroup is selected from the group consisting of pyridyl, pyrazinyl, andpyrimidinyl, R¹ represents hydrogen or straight-chain or branched alkylhaving 1 to 6 carbon atoms, R² represents hydrogen or straight-chain orbranched alkyl having 1 to 6 carbon atoms, Z represents halogen or NO₂,Hal represents halogen, X represents OR³, SR³, or NR⁴R⁵, Y representshydrogen, halogen, OR⁶, SR⁶, or NR⁷R⁸, R³ represents optionallysubstituted straight-chain or branched alkyl having 1 to 6 carbon atoms,optionally substituted straight-chain or branched alkenyl having 2 to 6carbon atoms, optionally substituted mono-, bi-, or tricyclic cycloalkylhaving 3 to 10 carbon atoms, or optionally substituted mono-, bi-, ortricyclic cycloalkylalkyl; or represents optionally substituted arylwherein the aryl group is selected from the group consisting of phenyl,naphthyl, tetrahydronaphthyl, indanyl, and fluorenyl, or optionallysubstituted arylalkyl having 6 or 10 carbon atoms in the aryl moiety and1 to 4 carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched, R⁴ and R⁵ independently of one anotherrepresent hydrogen; represent optionally substituted straight-chain orbranched alkyl having 1 to 6 carbon atoms, straight-chain or branchedalkenyl having 2 to 6 carbon atoms, straight-chain or branched alkynylhaving 2 to 6 carbon atoms, mono-, bi-, or tricyclic cycloalkyl having 3to 10 carbon atoms, mono-, bi-, or tricyclic cycloalkylalkyl, orstraight-chain or branched alkoxycarbonyl having I to 6 carbon atoms inthe alkoxy moiety; or represent optionally substituted aryl wherein thearyl group is selected from the group consisting of phenyl, naphthyl,tetrahydronaphthyl, indanyl, and fluorenyl, or optionally substitutedarylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched; or R⁴ and R⁵ together with the nitrogen atomto which they are attached represent an optionally substituted ring, R⁶represents optionally substituted straight-chain or branched alkylhaving 1 to 6 carbon atoms, optionally substituted straight-chain orbranched alkenyl having 2 to 6 carbon atoms, optionally substitutedmono-, bi-, or tricyclic cycloalkyl having 3 to 10 carbon atoms, oroptionally substituted mono-, bi-, or tricyclic cycloalkylalkyl; orrepresents optionally substituted aryl wherein the aryl group isselected from the group consisting of phenyl, naphthyl,tetrahydronaphthyl, indanyl, and fluorenyl, or optionally substitutedarylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched, and R⁷ and R⁸ independently of one anotherrepresent optionally substituted straight-chain or branched alkyl having1 to 6 carbon atoms, optionally substituted straight-chain or branchedalkenyl having 2 to 6 carbon atoms, optionally substituted mono-, bi-,or tricyclic cycloalkyl having 3 to 10 carbon atoms, or optionallysubstituted mono-, bi-, or tricyclic cycloalkylalkyl; or representoptionally substituted aryl wherein the aryl group is selected from thegroup consisting of phenyl, naphthyl, tetrahydronaphthyl, indanyl, andfluorenyl, or optionally substituted arylalkyl having 6 or 10 carbonatoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety inwhich the alkyl moiety is straight-chain or branched; or R7 and R8together with the nitrogen atom to which they are attached represent anoptionally substituted ring that is optionally interrupted by onenitrogen, oxygen, or sulphur atom, or R² and R³ together with the atomslinking them form an optionally C₁-C₄-alkyl-substitutedC₂-C₄-alkylidenediyl group.
 3. A composition for controlling animalpests comprising one or more compounds of formula (I) according to claim1 and one or more extenders and/or surfactants.
 4. A process forpreparing pesticides comprising mixing one or more compounds of formula(I) according to claim 1 with one or more extenders and/or surfactants.5. A compound of formula (I) according to claim 1 in which A representsoptionally substituted pyridyl, R¹ represents hydrogen or straight-chainor branched alkyl having 1 to 6 carbon atoms, R² represents hydrogen orstraight-chain or branched alkyl having 1 to 6 carbon atoms, Zrepresents halogen or NO₂, Hal represents halogen, X represents OR³,SR³, or NR⁴R^(5,) Y represents hydrogen, halogen, OR⁶, SR⁶, or NR⁷R^(8,)R3 represents optionally substituted straight-chain or branched alkylhaving 1 to 6 carbon atoms, optionally substituted straight-chain orbranched alkenyl having 2 to 6 carbon atoms, optionally substitutedmono-, bi-, or tricyclic cycloalkyl having 3 to 10 carbon atoms, oroptionally substituted mono-, bi-, or tricyclic cycloalkylalkyl; orrepresents optionally substituted aryl wherein the aryl group isselected from the group consisting of phenyl, naphthyl,tetrahydronaphthyl, indanyl, and fluorenyl, or optionally substitutedarylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched, R⁴ and R⁵ independently of one anotherrepresent hydrogen; represent optionally substituted straight-chain orbranched alkyl having 1 to 6 carbon atoms, straight-chain or branchedalkenyl having 2 to 6 carbon atoms, straight-chain or branched alkynylhaving 2 to 6 carbon atoms, mono-, bi-, or tricyclic cyclo-alkyl having3 to 10 carbon atoms, mono-, bi-, or tricyclic cycloalkylalkyl, orstraight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms inthe alkoxy moiety; or represent optionally substituted aryl wherein thearyl group is selected from the group consisting of phenyl, naphthyl,tetrahydronaphthyl, indanyl, and fluorenyl or optionally substitutedarylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched; or R⁴ and R⁵ together with the nitrogen atomto which they are attached represent an optionally substituted ring, R⁶represents optionally substituted straight-chain or branched alkylhaving 1 to 6 carbon atoms, optionally substituted straight-chain orbranched alkenyl having 2 to 6 carbon atoms, optionally substitutedmono-, bi-, or tricyclic cycloalkyl having 3 to 10 carbon atoms, oroptionally substituted mono-, bi-, or tricyclic cycloalkylalkyl; orrepresents optionally substituted aryl wherein the aryl group isselected from the group consisting of phenyl, naphthyl,tetrahydronaphthyl, indanyl, and fluorenyl, or optionally substitutedarylalkyl having 6 or 10 carbon atoms in the aryl moiety and 1 to 4carbon atoms in the alkyl moiety in which the alkyl moiety isstraight-chain or branched, and R⁷ and R⁸ independently of one anotherrepresent optionally substituted straight-chain or branched alkyl having1 to 6 carbon atoms, optionally substituted straight-chain or branchedalkenyl having 2 to 6 carbon atoms, optionally substituted mono-, bi-,or tricyclic cycloalkyl having 3 to 10 carbon atoms, or optionallysubstituted mono-, bi-, or tricyclic cycloalkylalkyl, or R⁷ and R⁸together with the nitrogen atom to which they are attached represent anoptionally substituted ring that is optionally interrupted by onenitrogen, oxygen, or sulphur atom, or R² and R³ together with the atomslinking them form an optionally C₁-C₄-alkyl-substitutedC₂-C₄-alkylidenediyl group.